EP0913198A1 - Verfahren zur Herstellung von Katalysatoren zur Verwendung in Umwandlungsreaktionen von organischen Verbindungen - Google Patents

Verfahren zur Herstellung von Katalysatoren zur Verwendung in Umwandlungsreaktionen von organischen Verbindungen Download PDF

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Publication number
EP0913198A1
EP0913198A1 EP98402678A EP98402678A EP0913198A1 EP 0913198 A1 EP0913198 A1 EP 0913198A1 EP 98402678 A EP98402678 A EP 98402678A EP 98402678 A EP98402678 A EP 98402678A EP 0913198 A1 EP0913198 A1 EP 0913198A1
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Prior art keywords
metal
catalyst
support
preparation
compound
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French (fr)
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EP0913198B1 (de
Inventor
Jean-Marie Basset
Jean-Pierre Candy
Blaise Didillon
Fabienne Le Peltier
Olivier Clause
Fatima Bentahar
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IFP Energies Nouvelles IFPEN
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321—Catalytic processes
    • C07C5/324—Catalytic processes with metals
    • C07C5/325—Catalytic processes with metals of the platinum group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
    • C07C5/3337—Catalytic processes with metals of the platinum group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/32—Manganese, technetium or rhenium
    • C07C2523/36—Rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium

Definitions

  • the present invention relates to a new process for the preparation of a catalyst containing at least one support, at least one metal from group VIII of the classification of the elements, and at least one additional element M chosen from the germanium, tin, lead, gallium, indium and thallium.
  • This catalyst can also contain another metal selected from the group consisting of alkali metals and / or a metalloid such as sulfur and / or any other chemical element such as halogen or a halogenated compound.
  • Patents and publications demonstrating that the addition of promoters to a metal of base improves the quality of the catalysts are very numerous. These are added in different forms such as salts or organometallic compounds. We generally obtains more active or more selective catalysts, sometimes more stable than the corresponding monometallic catalyst. The way these modifiers are introduced is not indifferent because it strongly conditions the properties of the catalyst.
  • Catalysts supported metal have been described in particular in US-A-3,998,900 and FR-A-2 495 605. They contain a metallic phase based on platinum, modified by an additional metal M such as tin, supported on inorganic oxides refractory such as alumina.
  • the introduction of the metal M is advantageously carried out using an organometallic compound of said metal M. This method of introduction of the metal M has already been described in US Pat. No. 3,531,543 and in the US Patent 4,548,918 to the applicant.
  • the processes already mentioned describe the manufacture of a catalyst by the use of minus an organometallic compound of the metal M.
  • the metal M is introduced under the form of at least one organometallic compound chosen from the group formed by complexes, in particular carbonyl, polyketone complexes of metals M and metal hydrocarbyls of metal M such as alkyls, cycloalkyls, aryls, akylaryl metals and arylalkyl metals.
  • the introduction of the additional element M in the form of a compound organometallic leads to more efficient catalysts but requires the use of an organic solvent.
  • the impregnating solvent described according to the technology of US patent 4,548,918 is selected from the group consisting of organic solvents oxygen containing 2 to 8 carbon atoms per molecule, and hydrocarbons paraffinic, naphthenic or aromatic containing essentially from 6 to 15 carbon atoms per molecule, and oxygenated organic compounds halogen containing 1 to 15 carbon atoms per molecule. These solvents can be used alone or mixed with each other.
  • the catalyst support according to the invention comprises at least one refractory oxide which is generally chosen from the metal oxides of groups IIA, IIIA, IIIB, IVA or IVB, of the periodic table of elements such as for example oxides of magnesium, aluminum, silicon, titanium, zirconium, thorium taken alone or mixed with each other or mixed with oxides of other elements of the periodic classification. Coal can also be used. We can also use zeolites or molecular sieves of type X, Y, mordenite, faujasite, ZSM-5, ZSM-4, ZSM-8, as well as mixtures of metal oxides from groups IIA, IIIA, IIIB, IVA and IVB with zeolitic material.
  • the preferred support is alumina, the specific surface of which is advantageously between 5 and 400 m 2 per gram, preferably between 50 and 350 m 2 per gram.
  • the preferred supports used in the field of transformation of organic functions are silica, carbon and alumina.
  • the catalyst may optionally additionally contain for example from 0.1 to 3% by weight of a halogen or halogenated compound. He can too contain 0.1 to 3% by weight of an alkali or alkaline earth metal. He can too optionally contain from 0.01 to 2% by weight of an element such as sulfur.
  • the catalyst can be prepared by different procedures for impregnating the support. and the invention is not limited to a specific impregnation procedure. When we uses several solutions, it is possible to carry out drying and / or calcinations intermediaries.
  • the additional element M can be introduced during the preparation of the support.
  • a method consists for example of kneading the wet support powder with the precursors of the catalyst and then to shape and dry.
  • bringing the element into contact organometallic M is characterized in that it is introduced into an aqueous solvent.
  • the additional metal M possibly introduced during the synthesis of the support according to a Sol-Gel type technique.
  • a mixed metal M-alumina gel can be obtained by hydrolyzing with an aqueous solution of an organometallic compound of metal M an organic solution of Al (OR ') 3 in a solvent such ROH or R'OH.
  • R and R ' can denote an alkyl group of methyl, ethyl, isopropyl, n-propyl, butyl type, or even a heavier group, such as n-hexyl.
  • the alcoholic solvent must be thoroughly dehydrated before the introduction of the aluminum alcoholate.
  • a heat treatment of the gel obtained operated at a temperature between 200 and 800 ° C, preferably between 300 and 700 ° C and even more preferably between 400 and 500 ° C, makes it possible to ensure the reaction complete of the water-soluble organometallic compound of the metal M with the gel, which causes the formation of the mixed oxide Al 2 O 3 -MO x .
  • the metal M can be added to an alumina sol.
  • US Patent 3,929,683 describes the introduction of tin in the form of a salt, for example SnCl 2 in an alumina sol.
  • a water-soluble organometallic compound of metal M to an alumina hydrosol, obtained for example by precipitating an acid solution of AlCl 3 at pH 4-5, then to promote the reaction of the compound of metal M with alumina hydrosol, for example under the effect of heat or a base.
  • the precursor of element M can be chosen, without this list being limiting, from the group of halogenated compounds, hydroxides. oxides, carbonates, and carboxylates of organometallic compounds of the element M. These compounds comprise at least one carbon-M bond.
  • the catalyst is obtained by impregnating the support, using an aqueous or organic solution at least one group VIII metal compound, the volume of the solution being preferably in excess of or equal to the retention volume of the support or equal to this volume.
  • the impregnated support is then filtered, optionally washed with distilled water then dried and calcined in air usually between 110 and about 500 ° C, then thereafter reduced under hydrogen at a temperature usually between about 200 and about 600 ° C and preferably between about 300 and about 500 ° C.
  • the product obtained is then impregnated with an aqueous solution of at least one tin compound, germanium, lead, rhenium, gallium, indium or thallium.
  • an aqueous solution of a compound is used tin carboxylate.
  • the volume of the aqueous solution is preferably equal to retention volume of the support and even more preferably in excess by compared to this volume.
  • the value of the concentration of at least one metal M in the aqueous solution is advantageously chosen between 0.01 and 25 mmol / l and so preferred between 0.5 and 20 mmol / l and even more preferably between 0.5 and 15 mmol / l.
  • the pH value of the aqueous solution is advantageously chosen between 10 and 14 and preferably between 10 and 12.
  • the product After having left the contact between the support impregnated with the metal of group VIII and the aqueous solution containing at least one compound of element M for several hours, the product is filtered, optionally washed with water and then dried.
  • the catalyst is obtained by impregnation of an aqueous solution of at least one compound of said metal M, the volume of the solution preferably being equal to the retention volume of the support and so even more preferred in excess relative to this volume.
  • an aqueous solution of a compound is used tin carboxylate.
  • the value of the concentration of at least one metal M in the aqueous solution is advantageously chosen between 0.01 and 25 mmol / l and so preferred between 0.5 and 20 mmol / l and even more preferably between 0.5 and 15 mmol / l.
  • the pH value of the aqueous solution is advantageously chosen between 10 and 14 and preferably between 10 and 12.
  • the product After leaving contact between the solid and the impregnation solution for several hours, the product is then dried. It usually ends with a calcination between 300 and 600 ° C, preferably by performing an air sweep for several hours.
  • the solid obtained is then impregnated with an aqueous or organic solution of at least one compound of group VIII metal, the volume of the solution preferably being excess or equal to the volume of retention of the support.
  • the product obtained After a few hours of contacting, the product obtained is then dried and then calcined in air between 300 and 600 ° C, preferably by performing an air sweep during many hours.
  • the catalyst Before use, the catalyst is reduced under hydrogen, for example between 20 and 600 ° C in order to obtain an active metallic phase.
  • the procedure for this treatment consists for example of a slow rise in temperature under current of hydrogen up to the maximum reduction temperature. understood for example between 20 and 600 ° C, and preferably between 90 and 500 ° C, followed by holding for for example for 1 to 6 hours at this temperature.
  • This reduction can be carried out immediately after a calcination, or later at the user. It is also possible to directly reduce the dried product directly to the user.
  • the catalyst prepared according to the invention can be used in a process for transformation of hydrocarbons involved in the refining and petrochemicals. It can also be used in a process in the field of chemistry.
  • Two catalysts A and B are prepared, each containing 0.7% by weight of platinum and 0.15% by weight of tin.
  • the support is a Degussa silica with a specific surface of 200 m 2 per gram.
  • the support is calcined at 500 ° C. in dry air for 5 hours and then brought into contact. with an ammoniacal solution (1 N) for 15 hours under nitrogen bubbling.
  • the platinum deposition is then carried out by introduction of a hydroxide solution platinum tetramine.
  • the suspension is then filtered, washed with distilled water and dried at 110 ° C under nitrogen flow.
  • the catalyst is then loaded into a reactor containing heptane under hydrogen.
  • the tetrabutyltin is then injected at 20 ° C. After 24 hours of reaction at temperature ambient in a hydrogen atmosphere, the solid is filtered, washed with heptane, then dried at 80 ° C. It is then reduced under a stream of hydrogen at 550 ° C for 4 hours.
  • Catalyst B is prepared from 3 grams of the solid at 0.7% by weight of platinum, reduced to 450 ° C. under a flow of hydrogen for 4 hours.
  • the catalyst is then loaded under hydrogen into a reactor containing 50 cm 3 of an aqueous ammonia solution (pH 11) containing 4.5 mg of tin in the form of tributyl tin acetate (Bu 3 SnOC (O) CH 3 ).
  • pH 11 aqueous ammonia solution
  • tributyl tin acetate Bu 3 SnOC (O) CH 3
  • the reaction mixture is filtered, washed and then dried at 80 ° C. It is then reduced under a stream of hydrogen at 550 ° C for 4 hours.
  • the support is prepared by hydrolysis with an aqueous solution of tributyl tin acetate (Bu 3 SnOC (O) CH 3 ) of a solution of aluminum isopropylate Al (OiPr) 3 in isopropanol, followed by a heat treatment at 450 ° C.
  • the platinum deposit is then obtained by dry impregnation of hexachloroplatinic acid in an amount of 0.7% by weight of platinum relative to the calcined support. After calcination at 450 ° C for a period of 12 hours, the catalyst is reduced under a stream of hydrogen at 500 ° C for 4 hours.
  • Catalysts A, B and C are subjected to an isobutane dehydrogenation test in an insulated tubular reactor. 1 g of catalyst is reduced at 550 ° C for 2 hours under a flow rate of 2 liters per hour of hydrogen. After injection of the charge the temperature is stabilized at 550 ° C. Gaseous effluent analysis is done online by gas chromatography.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP98402678A 1997-10-31 1998-10-27 Verfahren zur Herstellung von Katalysatoren zur Verwendung in Umwandlungsreaktionen von organischen Verbindungen Expired - Lifetime EP0913198B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9713684 1997-10-31
FR9713684A FR2770421B1 (fr) 1997-10-31 1997-10-31 Procede de preparation de catalyseurs utilisables dans les reactions de transformation de composes organiques

Publications (2)

Publication Number Publication Date
EP0913198A1 true EP0913198A1 (de) 1999-05-06
EP0913198B1 EP0913198B1 (de) 2005-04-13

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EP98402678A Expired - Lifetime EP0913198B1 (de) 1997-10-31 1998-10-27 Verfahren zur Herstellung von Katalysatoren zur Verwendung in Umwandlungsreaktionen von organischen Verbindungen

Country Status (9)

Country Link
US (1) US6281160B1 (de)
EP (1) EP0913198B1 (de)
JP (1) JP4374557B2 (de)
KR (1) KR100552314B1 (de)
CN (1) CN1108187C (de)
CA (1) CA2250374C (de)
DE (1) DE69829722T2 (de)
ES (1) ES2242266T3 (de)
FR (1) FR2770421B1 (de)

Cited By (1)

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EP1181978A1 (de) * 2000-08-23 2002-02-27 Institut Francais Du Petrole Bimetallischer Trägerkatalysator mit einer starken Interaktion zwischen einem Metall der Grupe VIII und Zinn und seine Verwendung für ein katalytisches Refomierungungsverfahren

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DE69829722T2 (de) 2005-09-01
FR2770421B1 (fr) 1999-12-10
ES2242266T3 (es) 2005-11-01
KR100552314B1 (ko) 2006-06-20
KR19990037511A (ko) 1999-05-25
CN1222406A (zh) 1999-07-14
CN1108187C (zh) 2003-05-14
EP0913198B1 (de) 2005-04-13
US6281160B1 (en) 2001-08-28
CA2250374A1 (fr) 1999-04-30
CA2250374C (fr) 2008-05-13
JPH11221464A (ja) 1999-08-17
DE69829722D1 (de) 2005-05-19
JP4374557B2 (ja) 2009-12-02
FR2770421A1 (fr) 1999-05-07

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